WO2005086178A1 - Element metallique revetu d'une couche de revetement comprenant un polymere essentiellement conducteur - Google Patents

Element metallique revetu d'une couche de revetement comprenant un polymere essentiellement conducteur Download PDF

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Publication number
WO2005086178A1
WO2005086178A1 PCT/EP2005/050846 EP2005050846W WO2005086178A1 WO 2005086178 A1 WO2005086178 A1 WO 2005086178A1 EP 2005050846 W EP2005050846 W EP 2005050846W WO 2005086178 A1 WO2005086178 A1 WO 2005086178A1
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WO
WIPO (PCT)
Prior art keywords
metal element
coating layer
self
group
conductive polymer
Prior art date
Application number
PCT/EP2005/050846
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English (en)
Inventor
Johan Vanbrabant
Original Assignee
Nv Bekaert Sa
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nv Bekaert Sa filed Critical Nv Bekaert Sa
Priority to EP20050716831 priority Critical patent/EP1721323A1/fr
Priority to CN2005800067585A priority patent/CN1926640B/zh
Priority to US10/591,537 priority patent/US20070190315A1/en
Priority to JP2007501272A priority patent/JP2007529620A/ja
Priority to BRPI0508453-9A priority patent/BRPI0508453A/pt
Publication of WO2005086178A1 publication Critical patent/WO2005086178A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C09D5/4476—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications comprising polymerisation in situ
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]

Definitions

  • the invention relates to a metal element coated with a coating layer comprising an inherently conductive polymer and at least one negative group.
  • the invention further relates to an article comprising at least one metal element embedded in a polymer material.
  • ICP's Inherently conductive polymers
  • chemical species in this case a metal substrate
  • a kinetic property in this case the kinetics of mass loss during a corrosion reaction
  • a species is said to be more reactive or to have a higher reactivity than some other (reference) species if it has a larger rate constant for a specified elementary reaction.
  • a fast indication of the reactivity can be found in the measurement of the corrosion potential, but a more reliable analysis is the measurement of the potential current relationship of a metal in a corrosive environment according to the Butler- Volmer relationship and/or as plotted in an Evans diagram.
  • the metal reactivity may be increased by machining, by increasing the surface roughness and/or by deforming the metal.
  • inherently conductive polymers can show an unacceptable adhesion to metal substrates and they offer only limited success as anti-corrosion coating on metal substrates. Summary of the invention.
  • a metal element coated at least partially with a self-assembled coating layer is provided.
  • the self-assembled coating layer comprises an inherently conductive polymer and at least one negative group.
  • the inherently conductive polymer is thereby functioning as a backbone structure for the negative group.
  • the inherently conductive polymer is functioning as a backbone structure for two or more negative groups.
  • a self-assembled coating layer means a coating layer spontaneously assembled from the monomers having a repetitive non-crystalline ordered structure.
  • the self-assembled coating layer is formed by electrochemical anodic polymerisation starting from a solution of a monomer of an inherently conductive polymer and at least one dopant.
  • the negative group of the self-assembled coating layer is derived from the dopant.
  • the inherently conductive polymer is polymerised on the metal element.
  • the inherently conductive polymer is polymerised in situ on the metal element.
  • in situ polymerisation is meant that the polymerisation occurs in the application bath comprising a monomer solution of an inherently conductive polymer and at least one dopant.
  • the metal element is thereby functioning as anode during polymerisation.
  • a great advantage of the in situ polymerisation is that the application of the coating can be done in line with other production steps such as cleaning or metal transformation such as drawing.
  • ICP's inherently conductive polymers
  • organic polymers that have poly-conjugated ⁇ electron systems (e.g. double bonds, aromatic or heteroaromatic rings or triple bonds). ICP's are able to conduct an electrical current due to a specific conjugated structure in the molecule.
  • ICP's are polyaniline, polypyrrole, polythiophene, polyphenylenevinylene, polydiacetylene, polyacetylene, polyquinoline, polyphenylenevinylene, polyheteroarylenvinylene and derivatives, copolymers and mixtures thereof.
  • any organic or inorganic negative group or molecule can be considered as for example groups or molecules having a negative charge or groups or molecules containing at least one atom which is nucleophilic oriented due to a free electronpair on the atom, resulting in a high electrondensity : e.g. oxygen, sulphur, nitrogen.
  • negative groups comprise for example phosphate, sulphate, chromate, molybdate, permanganate, silicate, nitrate, sulfonate, oxalate, formiate and thiol.
  • negative molecules having a high electrondensity comprise for example silanes, thiophenes, thiophthenes, organic sulfides, e.g. thiophenol.
  • the negative group is preferably a group interacting with the metal element in order to increase the corrosion resistance of the metal element by increasing the electrochemical potential of that specified metal.
  • the potential of the metal is increased until a passive behavior is reached; e.g. for steel preferred negative groups are phosphate, chromate or nitrate.
  • the corrosion resistance of the metal element is improved as the passivity of the metal element is increased.
  • the increased passivity amplifies the corrosion protection already generated by the inherently conductive polymer due to the increase of the potential into the passive area of the metal element.
  • the negative group or groups are preferably present in a concentration between 0.01 and 50 wt% of the coating layer. More preferably, the concentration of the negative group or groups is between 0.1 and 10 wt%.
  • the thickness of the self-assembled coating layer is preferably between 1 nm and 1000 nm, for example between 10 nm and 100 nrn.
  • the self-assembled coating according to the present invention has a low porosity.
  • porosity is defined as the percentage of coverage of the metal element with the self-assembled layer.
  • the porosity of the self-assembled layer can be determined based on electrochemical detection of iron dissolution of the substrate in an acidic medium.
  • Porosity analysis showed a porosity of less than 1 % for a self- assembled layer having a thickness of 100 nm. For a self-assembled layer having a thickness of 1000 nm no porosity was observed (porosity less than 0.001 %).
  • the self- assembled coating layer comprising an inherently conductive polymer and at least one negative group, can function as a backbone structure for a positive group such as a positive ion.
  • the self-assembled coating layer is functioning as a backbone structure for two or more positive groups.
  • the positive ion can be chosen to influence the properties of the coating layer, for example to optimise the adhesion characteristics of the coating layer to a polymer material in which the metal element is embedded.
  • the positive ion is preferably selected from the group consisting of the transition elements in the periodic table of elements, the earth alkali elements and the elements from group III and IV, such as Mg, Ca, Sr, Ba, V, Cr, Fe, Co, Ni, Cu, Zn, Zr, Mo, Cd, Ce, AI and Sn.
  • the selection of the positive ion is based on the polymer material to which it should react.
  • cobalt is a preferred ion.
  • Zinc can be preferred in case an increase in corrosion protection is desired.
  • the positive ion is preferably present in a concentration ranging between
  • the ion is present in a concentration between 0.04 to 0.15 wt %.
  • each positive ion is present in a concentration between 0.01 and 5 wt%.
  • the inherently conducting polymers used in the coating layer according to the present invention is used as a backbone structure for the negative group or groups and possibly also for the positive group.
  • the metal element may comprise an elongated metal element or a metal structure comprising at least one elongated metal element.
  • elongated metal element a metal wire, a metal cord, a metal tape or ribbon can be considered.
  • the elongated metal element may have any cross-section such as a circular, oval or flat (rectangular) cross-section.
  • the tensile strength of a metal element is preferably higher than 150O N/mm 2 .
  • the range of the tensile strength is for example between 15O0 and 4000 N/mm 2 . It may be desired to use metal cords having a structural elongation.
  • metal structure any structure comprising a number of elongated metal elements can be considered.
  • metal structures comprise woven, non-woven, braided, knitted or welded structures.
  • Any metal or metal alloy can be used to provide the metal elements of the composite article according to the invention.
  • the metals or metal alloys are selected from iron, titanium, aluminium, copper and alloys thereof.
  • Preferred alloys comprise high carbon or stainless steel alloys.
  • the metal element or the structure comprising a number of metal elements can be coated with one or more metal or metal alloy coating before the coating layer according to the present invention is applied.
  • Preferred metal or metal alloy coatings comprise zinc and zinc alloy coatings such as zinc-copper, zinc-aluminum, zinc-manganese, zinc- cobalt alloy, zinc-nickel alloy, zinc iron alloy or zinc-tin alloy coatings .
  • a preferred zinc-aluminum coating comprises a zinc coating comprising 2 to 10 % AI and possibly 0.1 to 0.4 % or a rare earth element such as La and/or Ce.
  • an article comprising a metal element as described above embedded in a polymer material.
  • Any thermoplastic material can be considered as polymer material.
  • examples comprise polyolefins such as polyethylene or polypropylene; polyamides; polyurethanes; polyesters; rubbers such as polyisoprene, chloroprene, styrene-butadiene, butyl rubber, nitrile and hydrogenetated nitrile rubbers, EPDM, ABS (acrylonitrile butadiene styrene) and PVC.
  • a method to coat a metal element with a self-assembled coating layer comprises electrochemical anodic polymerisation starting from a solution of a monomer of an inherently conductive polymer and at least one dopant.
  • the self-assembled coating layer comprises an inherently conductive polymer and at least one negative group.
  • the negative group is derived from the dopant.
  • the inherently conductive polymer is functioning as a backbone structure for the negative group.
  • the inherently conductive polymer is applied in situ on the metal element.
  • in situ polymerisation is meant that the polymerisation occurs in the application bath comprising a monomer solution of an inherently conductive polymer and at least one dopant.
  • the metal element is thereby functioning as anode during polymerisation.
  • a method to improve the corrosion resistance of a metal element is provided.
  • the method comprises applying a self-assembled layer on a metal element.
  • the self-assembled layer comprises an inherently conductive polymer and at least one negative group.
  • the inherently conductive polymer is functioning as a backbone structure for the negative group and the negative group is chosen in such a way to increase the corrosion resistance of the metal element.
  • the corrosion resistance of the metal element is improved as the passivity of the metal element is increased.
  • the increased passivity amplifies the corrosion protection already generated by the inherently conductive polymer due to the increase of the potential into the passive area of the metal element.
  • preferred negative groups are selected from the group consisting of phosphates, chromates, nitrates, oxalates, benzoates and citrates.
  • a method to improve the adhesion of a self-assembled layer applied on a metal element to a polymer material comprises applying a self-assembled layer on a metal element.
  • the self-assembled layer comprises an inherently conductive polymer and at least one negative group.
  • the self-assembled layer is functioning as a backbone structure for a positive ion or group.
  • the positive ion or group is chosen in such a way to increase the adhesion with the polymer material.
  • a method to improve the adhesion of a metal element to a polymer material is provided.
  • the method comprises the application of a self-assembled layer on a metal element and embedding this metal element with the self- assembled coating layer in a polymer material.
  • the self-assembled coating layer comprises an inherently conductive polymer and at least one negative group.
  • the self-assembled coating layer is functioning as a backbone structure for at least one positive group or ion.
  • the positive group or ion is chosen in such a way to improve the adhesion with the polymer material.
  • the polymer material comprises preferably a thermoplastic material.
  • Any thermoplastic material can be considered as polymer material.
  • Examples comprise polyolefins such as polyethylene or polypropylene; polyamides; polyurethanes; polyesters; rubbers such as polyisoprene, chloroprene, styrene-butadiene, butyl rubber, nitrile and hydrogenetated nitrile rubbers, EPDM, ABS (acrylonitrile butadiene styrene) and PVC.
  • the positive ion is preferably selected from the group consisting of the transition elements of the periodic table of ele ments, the earth alkali elements and the elements from group III and IV.
  • cobalt is a preferred ion.
  • FIG. 1 shows an example of a polymerisation reaction of a inherently conductive polymer
  • - Figure 2 shows an example of a polymerisation reaction whereby an inherently conductive polymer is functioning as a backbone structure for a negative group
  • - Figure 3 and 4 show two embodiments of the electrochemical in situ application of a coating layer according to the present invention
  • - Figure 5A to Figure 5D show metal elements coated with a coating layer according to the present invention.
  • Figure 1 shows an example of a polymerisation reaction :
  • step A comprises the electrochemical oxidation of the monomer 12 to form radical 14;
  • step B comprises the polymerisation of the monomer 14 to form the polymer 16 (polypyrrole).
  • Figure 2 shows the addition of a negative group 24 within the polymer structure 22 to form the structure 26 or 28.
  • thiophene ⁇ s added to a polypyrrole structure.
  • Thiophene is chosen to increase the adhesion of the metal element to the polymer (rubber) in which the metal element is embedded.
  • Figure 3 and 4 show two embodiments of the electrochemical in situ application of a coating layer according to the present invention.
  • Figure 3 shows a batch process for the application of the coating layer
  • Figure 4 shows a continuous process.
  • the substrate to be coated 34 is placed in a bath 31.
  • the bath comprises a solution 32 comprising an inherently conductive polymer and all other constituents of the coating layer.
  • a power source 33 is negatively connected to a counter electrode 36
  • the substrate to be coated 34 is functioning as anode.
  • Figure 4 shows a continuous method for the application of a coating layer according to the present invention on an elongated metal element such as a steel wire.
  • the steel wire 41 is introduced in a bath 42 thereby guided by rolls 43.
  • the bath 41 comprises a solution 44 comprising an inherently conductive polymer and all other constituents of the coating layer.
  • a power source 45 is negatively connected to a counter electrode 46
  • the steel wire 41 is functioning as anode.
  • Figure 5a shows a metal element 50 having an oxide layer 52.
  • the metal element is coated with a coating layer 54 according to the present invention.
  • the coating layer 54 comprises an ICP forming a backbone structure.
  • counter ions 55 are added to the backbone structure 54.
  • the coating layer 54 is further tailored by adding one ore more organic radical 56 such as thiophene in the backbone structure 54.
  • positive metal ions are added to further influence the characteristics of the coating layer.
  • Co 2+ is added to increase the adhesion of the coating layer 54 to rubber.
  • Some examples of steel wires with a coating layer according to the present invention are tested and are compared with a non-treated steel wire.
  • Examples 1 to 8 illustrate the influence of a coating layer according to the present invention on the corrosion resistance of a steel wire
  • examples 9 to 12 illustrate the influence of a coating layer according to the present invention to four different rubber compounds.
  • the steel wires are manufactured as follows. Starting from a rod wire, the wire is drawn in one or more steps until the desired diameter is obtained. Subsequently, the steel wires are coated with a coating layer according to the present invention by a method as shown in Figure 4.
  • the application solution is prepared starting from a monomer solution.
  • the solution can be made in an inorganic solvent such as water or in an organic solvent such as propylenecarbonate, acetonitrille, methanol, ethanol, propanol, aceton or other solvents.
  • the selection of the solvent depends upon the application. For certain metal elements, such as carbon steel substrates, water is preferred. For metal elements like aluminum, titanium or alloys like stainless steel organic solvents are preferred.
  • the corrosion behaviour of the tested steel wires is simulated and determined according to the standard procedure : Corrosion tests and standards : application and interpretation, ASTM MNL 20, pp. 75-80, ASTM G3-89, ASTM G5-82, ASTM G15-85a and ASTM STP 727.
  • ASTM MNL 20 pp. 75-80, ASTM G3-89, ASTM G5-82, ASTM G15-85a and ASTM STP 727.
  • Rp is measured. The higher the value of Rp, the better the corrosion resistance. Another parameter, next to the value of the polarisation resistance Rp, is the so-called “inhibition rating" as defined in "Compendium of Chemical
  • Example 1 comprises a non-treated steel wire.
  • the application solution comprises 0.1 M of ICP monomer pyrrole in water to which several negative groups are added.
  • the composition of the application solution of the different examples is shown in Table 1.
  • the steel wires are manufactured as described above.
  • the coating layer of examples 10 to 12 is applied by a method as shown in Figure 4.
  • the coating layer of example 10 is applied from an application solution comprising 0.1 M of ICP monomer pyrrole with 0.1 M oxalate.
  • the coating layer of example 11 and 12 is applied from an application solution comprising 0.1 M of ICP monomer pyrrole, 0.1 M oxalate and 0.1 M thiophene.
  • the bath circulation was high, whereas in example 12 the bath circulation was low.
  • Adhesion between the metal element and the polymer material is determined as follows. A non-treated steel wire and a steel wire coated with a coating layer according to the present invention are embedded in an industrial rubber composition. Subsequently, the rubber comprising the steel wires is vulcanised.
  • Both steel wires are pulled out from the vulcanised rubber.
  • the forces necessary to pull out the steel wires are measured. By comparing! the forces needed to pull out the "adherence loss rating" is determined.

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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne un élément métallique revêtu au moins partiellement d'une couche de revêtement autoassemblée, celle-ci comprenant un polymère essentiellement conducteur et au moins un groupe négatif. Ledit polymère essentiellement conducteur fonctionne comme une structure centrale du groupe négatif en question. L'invention concerne en outre un article comprenant au moins un tel élément métallique intégré dans un matériau polymère.
PCT/EP2005/050846 2004-03-04 2005-02-28 Element metallique revetu d'une couche de revetement comprenant un polymere essentiellement conducteur WO2005086178A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP20050716831 EP1721323A1 (fr) 2004-03-04 2005-02-28 Element metallique revetu d'une couche de revetement comprenant un polymere essentiellement conducteur
CN2005800067585A CN1926640B (zh) 2004-03-04 2005-02-28 涂布有包含本征导电聚合物的涂层的金属元件
US10/591,537 US20070190315A1 (en) 2004-03-04 2005-02-28 Metal element coated with a coating layer comprising an inherently conductive polymer
JP2007501272A JP2007529620A (ja) 2004-03-04 2005-02-28 固有導電性ポリマーを含むコーティング層で被覆した金属体
BRPI0508453-9A BRPI0508453A (pt) 2004-03-04 2005-02-28 elemento metálico revestido com uma camada de revestimento compreendendo um polìmero inerentemente condutor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP04100884 2004-03-04
EP04100884.8 2004-03-04

Publications (1)

Publication Number Publication Date
WO2005086178A1 true WO2005086178A1 (fr) 2005-09-15

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US (1) US20070190315A1 (fr)
EP (1) EP1721323A1 (fr)
JP (1) JP2007529620A (fr)
CN (1) CN1926640B (fr)
BR (1) BRPI0508453A (fr)
WO (1) WO2005086178A1 (fr)

Cited By (1)

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CN106884181A (zh) * 2017-04-18 2017-06-23 深圳氢爱天下健康科技控股有限公司 用以电解水的钛电极及其制备方法

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BRPI0508453A (pt) 2007-07-24
EP1721323A1 (fr) 2006-11-15

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